Functionalized polymers and improved tires therefrom

ABSTRACT

A method of forming a functionalized polymer, the method comprising reacting a living polymer with a compound defined by the formula 
                         
where R 5  includes a monovalent organic group, R 6  independently includes a monovalent organic group, each R 7  independently includes hydrogen or a monovalent organic group, each R 8  independently includes hydrogen or monovalent organic group, R 9  includes a monovalent organic group, M is silicon or tin, and x includes an integer from about 2 to about 10, where R 5  and R 6  may optionally each independently be alkoxy groups, and where R 7 , R 8 , and R 9  are non-Zerewitinoff organic groups.

This application gains benefit from U.S. Provisional Application No.60/644,168, filed Jan. 14, 2005, which is incorporated herein byreference.

FIELD OF THE INVENTION

One or more embodiments of this invention relate to functionalizedpolymers and their use in the manufacture of tires particularly tiretreads exhibiting reduced rolling resistance.

BACKGROUND OF THE INVENTION

In the art of making tires, it is desirable to employ rubbervulcanizates that demonstrate reduced hysteresis loss, i.e., less lossof mechanical energy to heat. Hysteresis loss is often attributed topolymer free ends within the cross-linked rubber network, as well as thedisassociation of filler agglomerates. The degree of dispersion offiller within the vulcanizate is also important, as increased dispersionprovides better wear resistance.

Functionalized polymers have been employed to reduce hysteresis loss andincrease bound rubber. The functional group of the functionalizedpolymer is believed to reduce the number of free chain ends viainteraction with filler particles. Also, the functional group isbelieved to reduce filler agglomeration, which thereby reduceshysteretic losses attributable to the disassociation of filleragglomerates (i.e., Payne effect).

Conjugated diene monomers are often anionically polymerized by usingalkyllithium compounds as initiators. Selection of certain alkyllithiumcompounds can provide a polymer product having functionality at the headof the polymer chain. A functional group can also be attached to thetail end of an anionically-polymerized polymer by terminating a livingpolymer with a functionalized compound.

For example, trialkyltin chlorides, such as tributyl tin chloride, havebeen employed to terminate the polymerization of conjugated dienes, aswell as the copolymerization of conjugated dienes and vinyl aromaticmonomers, to produce polymers having a trialkyltin functionality at thetail end of the polymer. These polymers have proven to betechnologically useful in the manufacture of tire treads that arecharacterized by improved traction, low rolling resistance, and improvedwear.

Because functionalized polymers are advantageous, especially in thepreparation of tire compositions, there exists a need for additionalfunctionalized polymers.

SUMMARY OF THE INVENTION

In general the present invention provides a method of forming afunctionalized polymer, the method comprising reacting a living polymerwith a compound defined by the formula

where R⁵ includes a monovalent organic group, R⁶ independently includesa monovalent organic group, each R⁷ independently includes hydrogen or amonovalent organic group, each R⁸ independently includes hydrogen ormonovalent organic group, R⁹ includes a monovalent organic group, M issilicon or tin, and x includes an integer from about 2 to about 10,where R⁵ and R⁶ may optionally each independently be alkoxy groups, andwhere R⁷, R⁸, and R⁹ are non-Zerewitinoff organic groups.

The present invention further provides a functionalized polymer definedby the formula:

where π includes a polymer chain, R¹ includes a monovalent organicgroup, R² includes a monovalent organic group or a hydroxy group, R³includes a divalent organic group, R⁴ includes a monovalent organicgroup, and M includes silicon (Si) or tin (Sn).

DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

The functionalized polymers that are useful in the manufacture of tiresinclude a primary or secondary amine group and a silicon-containing ortin-containing group at or near at least one end of a polymer chain. Inone embodiment, the functionalized polymers are employed in themanufacture of tire treads, and as a result tires having reduced rollingresistance can be prepared.

In one or more embodiments, the functionalized polymers can be definedby the formula I

where π includes a polymer chain, R¹ includes a monovalent organicgroup, R² includes a monovalent organic group or a hydroxy group, R³includes a divalent organic group, R⁴ includes a monovalent organicgroup, and M includes silicon (Si) or tin (Sn).

In one or more embodiments, the polymer chain (π) of the functionalizedpolymer includes an unsaturated polymer, which may also be referred toas a rubbery polymer. The polymer chain substituent can have a glasstransition temperature (T_(g)) that is less than 0° C., in otherembodiments less than −20° C., and in other embodiments less than −30°C. In one embodiment, the rubbery polymer chain exhibits a single glasstransition temperature.

Included are anionically polymerized polymers. Examples includepolybutadiene, polyisoprene, poly(styrene-co-butadiene),poly(styrene-co-butadiene-co-isoprene), poly(isoprene-co-styrene), andpoly(butadiene-co-isoprene).

In one or more embodiments, the polymer chain has a number averagemolecular weight (M_(n)) of from about 5 to about 1,000 kg/mole, inother embodiments from about 50 to about 500 kg/mole, and in otherembodiments 100 to about 300 kg/mole, as measured by using GelPermeation Chromatography (GPC) calibrated with polystyrene standardsand adjusted for the Mark-Houwink constants for the polymer in question.

In one or more embodiments, the monovalent organic groups may includehydrocarbyl groups or substituted hydrocarbyl groups such as, but notlimited to alkyl, cycloalkyl, substituted cycloalkyl, alkenyl,cycloalkenyl, substituted cycloalkenyl, aryl, allyl, substituted aryl,aralkyl, alkaryl, and alkynyl groups, with each group preferablycontaining from 1 carbon atom, or the appropriate minimum number ofcarbon atoms to form the group, up to 20 carbon atoms. These hydrocarbylgroups may contain heteroatoms such as, but not limited to, nitrogen,boron, oxygen, silicon, sulfur, and phosphorus atoms.

Alkoxy groups include hetero atom-containing organic groups. In one ormore embodiments, alkoxy groups can be defined by the formula —OR, whereR includes a monovalent organic group. In one embodiment, R is an alkylgroup including 1 to about 10 carbon atoms. For example, the alkoxygroup may include a methoxy, ethoxy, or propoxy group. In otherembodiments, the organic groups (or hydrocarbyl groups) are devoid ofhetero atoms that will render the group reactive with a living polymer.As an example, the group will not act as a leaving group in anucleophilic reaction. Those organic or hydrocarbyl groups that do notreact with living polymers may be referred to as non-Zerewitinofforganic groups or hydrocarbyl groups.

In one or more embodiments, divalent organic groups may include ahydrocarbylene group or substituted hydrocarbylene group such as, butnot limited to, alkylene, cycloalkylene, substituted alkylene,substituted cycloalkylene, alkenylene, cycloalkenylene, substitutedalkenylene, substituted cycloalkenylene, arylene, and substitutedarylene groups, with each group preferably containing from 1 carbonatom, or the appropriate minimum number of carbon atoms to form thegroup, up to about 20 carbon atoms. Substituted hydrocarbylene groupincludes a hydrocarbylene group in which one or more hydrogen atoms havebeen replaced by a substituent such as an alkyl group. The divalentorganic groups may also contain one or more heteroatoms such as, but notlimited to, nitrogen, oxygen, boron, silicon, sulfur, and phosphorusatoms. In one or more embodiments, the divalent organic group will notreact with a living polymer.

In one or more embodiments, R¹ and R² may each individually be an alkylgroup including from about 1 to about 10 carbon atoms, and in otherembodiments include less than 7 carbon atoms. In certain embodiments, R¹and R² may each individually be an alkoxy group including from about 1to about 10 carbon atoms, and in other embodiments include alkoxy groupsincluding less than 7 carbon atoms. In one or more embodiments, one ofR¹ and R² is an alkyl group and the other of R¹ and R² is an alkoxygroup.

In one or more embodiments, R³ is an alkylene or substituted alkylenegroup including from about 1 to about 10 carbon atoms, and in otherembodiments less than 7 carbon atoms.

In one or more embodiments, R⁴ is an alkyl group including from 1 toabout 20 carbon atoms, in other embodiments, less than 12 carbon atoms,and in other embodiments less than 8 carbon atoms.

In one or more embodiments, the functionalized polymer includes afunctional group at the head of the polymer; i.e., at an end other thanthat including the tin or silicon atom or functionality. Thisfunctionalized polymer can be defined by the formula II

where α is a functionality or functional group that reacts or interactswith rubber or rubber fillers or otherwise has a desirable impact onfilled rubber compositions or vulcanizates, π, R¹, R², R³, and R⁴ are asdescribed above, and M includes silicon (Si) or tin (Sn). In one or moreembodiments, α reduces the 50° C. hysteresis loss of vulcanizatesincluding the functionalized polymer when compared to similarvulcanizates with polymer not including α (i.e., a comparable polymerwithout α).

Those groups or substituents that react or interact with rubber orrubber fillers or otherwise have a desirable impact on filled rubbercompositions or vulcanizates are known and may include trialkyl tinsubstituents, cyclic amine groups, or aryl or alkyl thio acetals.Exemplary trialkyl tin substituents are disclosed in U.S. Pat. No.5,268,439, which is incorporated herein by reference. Exemplary cyclicamine groups are disclosed in U.S. Pat. Nos. 6,080,853, 5,786,448,6,025,450, and 6,046,288, which are incorporated herein by reference.Exemplary aryl or alkyl thio acetals (e.g., dithianes) are disclosed inInternational Publication No. WO 2004/041870, which is incorporatedherein by reference.

In one embodiment, the functionalized polymers may be prepared byreacting or terminating a living polymer with an cyclicaminoheterocompound, which may also be referred to as a cyclic azagilacycle orcyclic azastannacycle (they may also be referred to simply as afunctionalizing agent).

In one embodiment, the cyclicaminohetero compound may be defined by theformula III

where R⁵ includes a monovalent organic group, R⁶ independently includesa monovalent organic group, each R⁷ independently includes hydrogen or amonovalent organic group, each R⁸ independently includes hydrogen ormonovalent organic group, R⁹ includes a monovalent organic group, M issilicon or tin, and x includes an integer from about 2 to about 10,where R⁵ and R⁶ may optionally each independently be alkoxy groups, andwhere R⁷, R⁸, and R⁹ are non-Zerewitinoff organic groups.

In one or more embodiments, R⁵ and R⁶ may each individually be an alkylgroup including from about 1 to about 10 carbon atoms, and in otherembodiments include less than 7 carbon atoms. In certain embodiments, R⁵and R⁶ may each individually be an alkoxy group including from about 1to about 10 carbon atoms, and in other embodiments include alkoxy groupsincluding less than 7 carbon atoms. In one or more embodiments, one ofR⁵ and R⁶ is an alkyl group and the other of R⁵ and R⁶ is an alkoxygroup.

In one or more embodiments, R⁷ and R⁸ may each individually be an alkylgroup including less than 10 carbon atoms, and in other embodimentsinclude less than 7 carbon atoms. In certain embodiments, R⁷ and R⁸ areboth hydrogen. In other embodiments, one of R⁷ and R⁸ is hydrogen andthe other of R⁷ and R⁸ is an alkyl group.

In one or more embodiments, R⁹ is an alkyl group including from 1 toabout 20 carbon atoms, in other embodiments, less than 12 carbon atoms,and in other embodiments less than 8 carbon atoms.

Useful types of compounds include cyclicaminodialkoxysilanes,cyclicaminodialkoxystannanes, cyclicaminodialkylsilanes,cyclicaminodialkylstannanes, cyclicaminoaklylalkoxysilanes,cyclicaminoalkylalkoxystannanes, and mixtures thereof. The dialkyl anddialkoxy compounds include those compounds where the substituents of thehetero atom (i.e., R⁵ and R⁶) are either both alkoxy groups or bothalkyl groups. The alkylalkoxy compounds include those compounds whereone of the substituents of the hetero atom is alkoxy and the other isalkyl.

Examples of cyclicaminodialkoxysilanes includeN-methyl-aza-2,2-dimethoxysilacyclopentane,N-ethyl-aza-2,2-dimethoxysilacyclopentane,N-n-propyl-aza-2,2-dimethoxysilacyclopentane,N-n-butyl-aza-2,2-dimethoxysilacyclopentane,N-methyl-aza-2,2-diethoxysilacyclopentane,N-ethyl-aza-2,2-diethoxysilacyclopentane,N-n-propyl-aza-2,2-diethoxysilacyclopentane,N-n-butyl-aza-2,2-diethoxysilacyclopentane,N-methyl-aza-2,2-dipropoxysilacyclopentane,N-ethyl-aza-2,2-dipropoxysilacyclopentane,N-n-propyl-aza-2,2-dipropoxysilacyclopentane,N-n-butyl-aza-2,2-dipropoxysilacyclopentane,N-methyl-aza-2,2-dibutoxysilacyclopentane,N-ethyl-aza-2,2-dibutoxysilacyclopentane,N-n-propyl-aza-2,2-dibutoxysilacyclopentane,N-n-butyl-aza-2,2-dibutoxysilacyclopentane,N-methyl-aza-2-ethoxy-2-methoxysilacyclopentane,N-ethyl-aza-2-butoxy-2-ethoxysilacyclopentane,N-n-propyl-aza-2-methoxy-2-propoxysilacyclopentane,N-n-butyl-aza-2-propoxy-2-ethoxysilacyclopentane,N-methyl-aza-2-butoxy-2-methoxysilacyclopentane,N-ethyl-aza-2-propoxy-2-ethoxysilacyclopentane,N-n-propyl-aza-2-butoxy-2-propoxysilacyclopentane,N-n-butyl-aza-2-methoxy-2-ethoxysilacyclopentane,N-methyl-aza-2,2-dimethoxysilacyclobutane,N-ethyl-aza-2,2-dimethoxysilacyclobutane,N-n-propyl-aza-2,2-dimethoxysilacyclobutane,N-n-butyl-aza-2,2-dimethoxysilacyclobutane,N-methyl-aza-2,2-diethoxysilacyclobutane,N-ethyl-aza-2,2-diethoxysilacyclobutane,N-n-propyl-aza-2,2-diethoxysilacyclobutane,N-n-butyl-aza-2,2-diethoxysilacyclobutane,N-methyl-aza-2,2-dipropoxysilacyclobutane,N-ethyl-aza-2,2-dipropoxysilacyclobutane,N-n-propyl-aza-2,2-dipropoxysilacyclobutane,N-n-butyl-aza-2,2-dipropoxysilacyclobutane,N-methyl-aza-2,2-dibutoxysilacyclobutane,N-ethyl-aza-2,2-dibutoxysilacyclobutane,N-n-propyl-aza-2,2-dibutoxysilacyclobutane,N-n-butyl-aza-2,2-dibutoxysilacyclobutane,N-methyl-aza-2-ethoxy-2-methoxysilacyclobutane,N-ethyl-aza-2-butoxy-2-ethoxysilacyclobutane,N-n-propyl-aza-2-methoxy-2-propoxysilacyclobutane,N-n-butyl-aza-2-propoxy-2-ethoxysilacyclobutane,N-methyl-aza-2-butoxy-2-methoxysilacyclobutane,N-ethyl-aza-2-propoxy-2-ethoxysilacyclobutane,N-n-propyl-aza-2-butoxy-2-propoxysilacyclobutane,N-n-butyl-aza-2-methoxy-2-ethoxysilacyclobutane,N-methyl-aza-2,2-dimethoxysilacyclohexane,N-ethyl-aza-2,2-dimethoxysilacyclohexane,N-n-propyl-aza-2,2-dimethoxysilacyclohexane,N-n-butyl-aza-2,2-dimethoxysilacyclohexane,N-methyl-aza-2,2-diethoxysilacyclohexane,N-ethyl-aza-2,2-diethoxysilacyclohexane,N-n-propyl-aza-2,2-diethoxysilacyclohexane,N-n-butyl-aza-2,2-diethoxysilacyclohexane,N-methyl-aza-2,2-dipropoxysilacyclohexane,N-ethyl-aza-2,2-dipropoxysilacyclohexane,N-n-propyl-aza-2,2-dipropoxysilacyclohexane,N-n-butyl-aza-2,2-dipropoxysilacyclohexane,N-methyl-aza-2,2-dibutoxysilacyclohexane,N-ethyl-aza-2,2-dibutoxysilacyclohexane,N-n-propyl-aza-2,2-dibutoxysilacyclohexane,N-n-butyl-aza-2,2-dibutoxysilacyclohexane,N-methyl-aza-2-ethoxy-2-methoxysilacyclohexane,N-ethyl-aza-2-butoxy-2-ethoxysilacyclohexane,N-n-propyl-aza-2-methoxy-2-propoxysilacyclohexane,N-n-butyl-aza-2-propoxy-2-ethoxysilacyclohexane,N-methyl-aza-2-butoxy-2-methoxysilacyclohexane,N-ethyl-aza-2-propoxy-2-ethoxysilacyclohexane,N-n-propyl-aza-2-butoxy-2-propoxysilacyclohexane, orN-n-butyl-aza-2-methoxy-2-ethoxysilacyclohexane.

In addition to the foregoing, the silacycloheptane, and silacyclooctane,and silacyclononane derivatives of these silane compounds are useful andare contemplated by the present invention. Also, the equivalentstannanes are also contemplated, and their names can be derived by thoseskilled in the art without undo calculation or experimentation. Forexample, the equivalent stannane toN-n-butyl-aza-2-methoxy-2-ethoxysilacyclohexane isN-n-butyl-aza-2-methoxy-2-ethoxystannacyclohexane.

Examples of cycliaminodialkylsilanes includeN-methyl-aza-2,2-dimethylsilacyclopentane,N-ethyl-aza-2,2-dimethylsilacyclopentane,N-n-propyl-aza-2,2-dimethylsilacyclopentane,N-n-butyl-aza-2,2-dimethylsilacyclopentane,N-methyl-aza-2,2-diethylsilacyclopentane,N-ethyl-aza-2,2-diethylsilacyclopentane,N-n-propyl-aza-2,2-diethylsilacyclopentane,N-n-butyl-aza-2,2-diethylsilacyclopentane,N-methyl-aza-2,2-dipropylsilacyclopentane,N-ethyl-aza-2,2-dipropylsilacyclopentane,N-n-propyl-aza-2,2-dipropylsilacyclopentane,N-n-butyl-aza-2,2-dipropylsilacyclopentane,N-methyl-aza-2,2-dibutylsilacyclopentane,N-ethyl-aza-2,2-dibutylsilacyclopentane,N-n-propyl-aza-2,2-dibutylsilacyclopentane,N-n-butyl-aza-2,2-dibutylsilacyclopentane,N-methyl-aza-2-ethyl-2-methylsilacyclopentane,N-ethyl-aza-2-butyl-2-ethylsilacyclopentane,N-n-propyl-aza-2-methyl-2-propylsilacyclopentane,N-n-butyl-aza-2-propyl-2-ethylsilacyclopentane,N-methyl-aza-2-butyl-2-methylsilacyclopentane,N-ethyl-aza-2-propyl-2-ethylsilacyclopentane,N-n-propyl-aza-2-butyl-2-propylsilacyclopentane,N-n-butyl-aza-2-methyl-2-ethylsilacyclopentane,N-methyl-aza-2,2-dimethylsilacyclobutane,N-ethyl-aza-2,2-dimethylsilacyclobutane,N-n-propyl-aza-2,2-dimethylsilacyclobutane,N-n-butyl-aza-2,2-dimethylsilacyclobutane,N-methyl-aza-2,2-diethylsilacyclobutane,N-ethyl-aza-2,2-diethylsilacyclobutane,N-n-propyl-aza-2,2-diethylsilacyclobutane,N-n-butyl-aza-2,2-diethylsilacyclobutane,N-methyl-aza-2,2-dipropylsilacyclobutane,N-ethyl-aza-2,2-dipropylsilacyclobutane,N-n-propyl-aza-2,2-dipropylsilacyclobutane,N-n-butyl-aza-2,2-dipropylsilacyclobutane,N-methyl-aza-2,2-dibutylsilacyclobutane,N-ethyl-aza-2,2-dibutylsilacyclobutane,N-n-propyl-aza-2,2-dibutylsilacyclobutane,N-n-butyl-aza-2,2-dibutylsilacyclobutane,N-methyl-aza-2-ethyl-2-methylsilacyclobutane,N-ethyl-aza-2-butyl-2-ethylsilacyclobutane,N-n-propyl-aza-2-methyl-2-propylsilacyclobutane,N-n-butyl-aza-2-propyl-2-ethylsilacyclobutane,N-methyl-aza-2-butyl-2-methylsilacyclobutane,N-ethyl-aza-2-propyl-2-ethylsilacyclobutane,N-n-propyl-aza-2-butyl-2-propylsilacyclobutane,N-n-butyl-aza-2-methyl-2-ethylsilacyclobutane,N-methyl-aza-2,2-dimethylsilacyclohexane,N-ethyl-aza-2,2-dimethylsilacyclohexane,N-n-propyl-aza-2,2-dimethylsilacyclohexane,N-n-butyl-aza-2,2-dimethylsilacyclohexane,N-methyl-aza-2,2-diethylsilacyclohexane,N-ethyl-aza-2,2-diethylsilacyclohexane,N-n-propyl-aza-2,2-diethylsilacyclohexane,N-n-butyl-aza-2,2-diethylsilacyclohexane,N-methyl-aza-2,2-dipropylsilacyclohexane,N-ethyl-aza-2,2-dipropylsilacyclohexane,N-n-propyl-aza-2,2-dipropylsilacyclohexane,N-n-butyl-aza-2,2-dipropylsilacyclohexane,N-methyl-aza-2,2-dibutylsilacyclohexane,N-ethyl-aza-2,2-dibutylsilacyclohexane,N-n-propyl-aza-2,2-dibutylsilacyclohexane,N-n-butyl-aza-2,2-dibutylsilacyclohexane,N-methyl-aza-2-ethyl-2-methylsilacyclohexane,N-ethyl-aza-2-butyl-2-ethylsilacyclohexane,N-n-propyl-aza-2-methyl-2-propylsilacyclohexane,N-n-butyl-aza-2-propyl-2-ethylsilacyclohexane,N-methyl-aza-2-butyl-2-methylsilacyclohexane,N-ethyl-aza-2-propyl-2-ethylsilacyclohexane,N-n-propyl-aza-2-butyl-2-propylsilacyclohexane, orN-n-butyl-aza-2-methyl-2-ethylsilacyclohexane.

In addition to the foregoing, the silacycloheptane, and silacyclooctane,and silacyclononane derivatives of these silane compounds are useful andare contemplated by the present invention. Also, the equivalentstannanes are also contemplated, and their names can be derived by thoseskilled in the art without undo calculation or experimentation. Forexample, the equivalent stannane toN-n-butyl-aza-2-methyl-2-ethylsilacyclohexane isN-n-butyl-aza-2-methyl-2-ethylstannacyclohexane.

Examples of cyclicaminoalkoxyalkylsilanes includeN-methyl-aza-2-methoxy-2-methylsilacyclopentane,N-ethyl-aza:2-methoxy-2-methylsilacyclopentane,N-n-propyl-aza-2-methoxy-2-methylsilacyclopentane,N-n-butyl-aza-2-methoxy-2-methylsilacyclopentane,N-methyl-aza-2-ethoxy-2-ethylsilacyclopentane,N-ethyl-aza-2-ethoxy-2-ethylsilacyclopentane,N-n-propyl-aza-2-ethoxy-2-ethylsilacyclopentane,N-n-butyl-aza-2-ethoxy-2-ethylsilacyclopentane,N-methyl-aza-2-propoxy-2-propylsilacyclopentane,N-ethyl-aza-2-propoxy-2-propylsilacyclopentane,N-n-propyl-aza-2-propoxy-2-propylsilacyclopentane,N-n-butyl-aza-2-propoxy-2-propylsilacyclopentane,N-methyl-aza-2-propoxy-2-butylsilacyclopentane,N-ethyl-aza-2-propoxy-2-butylsilacyclopentane,N-n-propyl-aza-2-propoxy-2-butylsilacyclopentane,N-n-butyl-aza-2-propoxy-2-butylsilacyclopentane,N-methyl-aza-2-ethoxy-2-methylsilacyclopentane,N-ethyl-aza-2-butoxy-2-ethylsilacyclopentane,N-n-propyl-aza-2-methoxy-2-propylsilacyclopentane,N-n-butyl-aza-2-propoxy-2-ethylsilacyclopentane,N-methyl-aza-2-butoxy-2-methylsilacyclopentane,N-ethyl-aza-2-propoxyl-2-ethylsilacyclopentane,N-n-propyl-aza-2-butoxy-2-propylsilacyclopentane,N-n-butyl-aza-2-methoxy-2-ethylsilacyclopentane,N-methyl-aza-2-methoxy-2-methylsilacyclobutane,N-ethyl-aza-2-methoxy-2-methylsilacyclobutane,N-n-propyl-aza-2-methoxy-2-methylsilacyclobutane,N-n-butyl-aza-2-methoxy-2-methylsilacyclobutane,N-methyl-aza-2-ethoxy-2-ethylsilacyclobutane,N-ethyl-aza-2-ethoxy-2-ethylsilacyclobutane,N-n-propyl-aza-2-ethoxy-2-ethylsilacyclobutane,N-n-butyl-aza-2-ethoxy-2-ethylsilacyclobutane,N-methyl-aza-2-propoxy-2-propylsilacyclobutane,N-ethyl-aza-2-propoxy-2-propylsilacyclobutane,N-n-propyl-aza-2-propoxy-2-propylsilacyclobutane,N-n-butyl-aza-2-propoxy-2-propylsilacyclobutane,N-methyl-aza-2-butoxy-2-butylsilacyclobutane,N-ethyl-aza-2-butoxy-2-butylsilacyclobutane,N-n-propyl-aza-2-butoxy-2-butylsilacyclobutane,N-n-butyl-aza-2-butoxy-2-butylsilacyclobutane,N-methyl-aza-2-ethoxy-2-methylsilacyclobutane,N-ethyl-aza-2-butoxy-2-ethylsilacyclobutane,N-n-propyl-aza-2-methoxy-2-propylsilacyclobutane,N-n-butyl-aza-2-propoxy-2-ethylsilacyclobutane,N-methyl-aza-2-butoxy-2-methylsilacyclobutane,N-ethyl-aza-2-propoxy-2-ethylsilacyclobutane,N-n-propyl-aza-2-butoxy-2-propylsilacyclobutane,N-n-butyl-aza-2-methoxy-2-ethylsilacyclobutane,N-methyl-aza-2-methoxy-2-methylsilacyclohexane,N-ethyl-aza-2-methoxy-2-methylsilacyclohexane,N-n-propyl-aza-2-methoxy-2-methylsilacyclohexane,N-n-butyl-aza-2-methoxy-2-methylsilacyclohexane,N-methyl-aza-2-ethoxy-2-ethylsilacyclohexane,N-ethyl-aza-2-ethoxy-2-ethylsilacyclohexane,N-n-propyl-aza-2-ethoxy-2-ethylsilacyclohexane,N-n-butyl-aza-2-ethoxy-2-ethylsilacyclohexane,N-methyl-aza-2-propoxy-2-propylsilacyclohexane,N-ethyl-aza-2-propoxy-2-propylsilacyclohexane,N-n-propyl-aza-2-propoxy-2-propylsilacyclohexane,N-n-butyl-aza-2-propoxy-2-propylsilacyclohexane,N-methyl-aza-2-butoxy-2-butylsilacyclohexane,N-ethyl-aza-2-butoxy-2-butylsilacyclohexane,N-n-propyl-aza-2-butoxy-2-butylsilacyclohexane,N-n-butyl-aza-2-butoxy-2-butylsilacyclohexane,N-methyl-aza-2-ethoxy-2-methylsilacyclohexane,N-ethyl-aza-2-butoxy-2-ethylsilacyclohexane,N-n-propyl-aza-2-methoxy-2-propylsilacyclohexane,N-n-butyl-aza-2-propoxy-2-ethylsilacyclohexane,N-methyl-aza-2-butoxyl-2-methylsilacyclohexane,N-ethyl-aza-2-propoxy-2-ethylsilacyclohexane,N-n-propyl-aza-2-butoxyl-2-propylsilacyclohexane, orN-n-butyl-aza-2-methoxy-2-ethylsilacyclohexane.

In addition to the foregoing, the silacycloheptane, and silacyclooctane,and silacyclononane derivatives of these silane compounds are useful andare contemplated by the present invention. Also, the equivalentstannanes are also contemplated, and their names can be derived by thoseskilled in the art without undo calculation or experimentation. Forexample, the equivalent stannane toN-n-butyl-aza-2-methoxy-2-ethylsilacyclohexane isN-n-butyl-aza-2-methoxy-2-ethylstannacyclohexane.

In one ore more embodiments, living polymers include anionicallypolymerized polymers. Anionically-polymerized living polymers may beformed by reacting anionic initiators with certain unsaturated monomersto propagate a polymeric structure. Throughout formation and propagationof the polymer, the polymeric structure may be anionic and “living.” Anew batch of monomer subsequently added to the reaction can add to theliving ends of the existing chains and increase the degree ofpolymerization. A living polymer, therefore, includes a polymericsegment having a living or reactive end. Anionic polymerization isfurther described in George Odian, Principles of Polymerization, ch. 5(3^(rd) Ed. 1991), or Panek, 94 J. Am. Chem. Soc., 8768 (1972), whichare incorporated herein by reference.

Monomers that can be employed in preparing an anionically polymerizedliving polymer include any monomer capable of being polymerizedaccording to anionic polymerization techniques. These monomers includethose that lead to the formation of elastomeric homopolymers orcopolymers. Suitable monomers include, without limitation, conjugatedC₄-C₁₂ dienes, C₈-C₁₈ monovinyl aromatic monomers, and C₆-C₂₀ trienes.Examples of conjugated diene monomers include, without limitation,1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, and1,3-hexadiene. A non-limiting example of trienes includes myrcene.Aromatic vinyl monomers include, without limitation, styrene, a-methylstyrene, p-methylstyrene, and vinylnaphthalene. When preparingelastomeric copolymers, such as those containing conjugated dienemonomers and aromatic vinyl monomers, the conjugated diene monomers andaromatic vinyl monomers are normally used at a ratio of 95:5 to 50:50,and preferably 95:5 to 65:35.

Any anionic initiator can be employed to initiate the formation andpropagation of the living polymers. Exemplary anionic initiatorsinclude, but are not limited to, alkyl lithium initiators such asn-butyl lithium, arenyllithium initiators, arenylsodium initiators,aminoalkyllithiums, and alkyl tin lithiums. Other useful initiatorsinclude N-lithiohexamethyleneimide, N-lithiopyrrolidinide, andN-lithiododecamethyleneimide as well as organolithium compounds such asthe tri-alkyl lithium adducts of substituted aldimines and substitutedketimines, and N-lithio salts of substituted secondary amines. Stillothers include alkylthioacetals (e.g., dithianes). Exemplary initiatorsare also described in the following U.S. Pat. Nos. 5,332,810, 5,329,005,5,578,542, 5,393,721, 5,698,646, 5,491,230, 5,521,309, 5,496,940,5,574,109, 5,786,441, and International Publication Nos. WO 2004/020475and WO 2004/041870, which are incorporated herein by reference.

The amount of initiator employed in conducting anionic polymerizationscan vary widely based upon the desired polymer characteristics. In oneor more embodiments, from about 0.1 to about 100, and optionally fromabout 0.33 to about 10 mmol of lithium per 100 g of monomer is employed.

Anionic polymerizations are typically conducted as a solutionpolymerization in a polar solvent such as tetrahydrofuran (THF) or anonpolar hydrocarbon such as the various cyclic and acyclic hexanes,heptanes, octanes, pentanes, their alkylated derivatives, and mixturesthereof, as well as benzene.

In order to promote randomization in copolymerization and to controlvinyl content, a polar coordinator may be added to the polymerizationingredients. Amounts range between 0 and 90 or more equivalents perequivalent of lithium. The amount depends on the amount of vinyldesired, the level of styrene employed and the temperature of thepolymerization, as well as the nature of the specific polar coordinator(modifier) employed. Suitable polymerization modifiers include, forexample, ethers or amines to provide the desired microstructure andrandomization of the comonomer units.

Compounds useful as polar coordinators include those having an oxygen ornitrogen heteroatom and a non-bonded pair of electrons. Examples includedialkyl ethers of mono and oligo alkylene glycols; “crown” ethers;tertiary amines such as tetramethylethylene diamine (TMEDA); linear THFoligomers; and the like. Specific examples of compounds useful as polarcoordinators include tetrahydrofuran (THF), linear and cyclic oligomericoxolanyl alkanes such as 2,2-bis(2′-tetrahydrofuryl) propane,di-piperidyl ethane, dipiperidyl methane, hexamethylphosphoramide,N-N′-dimethylpiperazine, diazabicyclooctane, dimethyl ether, diethylether, tributylamine and the like. The linear and cyclic oligomericoxolanyl alkane modifiers are described in U.S. Pat. No. 4,429,091,incorporated herein by reference.

Anionically polymerized living polymers can be prepared by either batchor continuous methods. A batch polymerization is begun by charging ablend of monomer(s) and normal alkane solvent to a suitable reactionvessel, followed by the addition of the polar coordinator (if employed)and an initiator compound. The reactants are heated to a temperature offrom about 20 to about 130° C. and the polymerization is allowed toproceed for from about 0.1 to about 24 hours. This reaction produces areactive polymer having a reactive or living end. Preferably, at leastabout 30% of the polymer molecules contain a living end. Morepreferably, at least about 50% of the polymer molecules contain a livingend. Even more preferably, at least about 80% contain a living end.

In one or more embodiments, the functionalizing agent (e.g.,cyclicaminoalkoxysilane) is reacted with the living polymer end. Thisreaction can be achieved by simply mixing the functionalizing agent withthe living polymer. The reaction may occur in solution; for example, thefunctionalizing agent may be added to the solution containing the livingpolymer. Without intending to be bound to any particular theory, it isbelieved that the anionic-living polymer reacts with thecyclicaminohetero compound via a nucleophilic substitution reaction.This reaction can include the displacement of an alkoxy group from thehetero atom of the cyclicaminohetero compound or the displacement of thenitrogen-hetero bond within the cyclicaminohetero compound.

In one embodiment, the functionalizing agent may be added to the livingpolymer cement (i.e., polymer and solvent) once a peak polymerizationtemperature, which is indicative of nearly complete monomer conversion,is observed. Because live ends may self-terminate, the functionalizingagent may be added within about 25 to 35 minutes of the peakpolymerization temperature.

The amount of functionalizing agent employed to prepare thefunctionalized polymers is best described with respect to theequivalents of lithium or metal cation associated with the initiator.For example, where a lithium initiator is employed, the moles offunctionalizing agent per mole of lithium may be about 0.3 to about 2,optionally from about 0.6 to about 1.5, optionally from about 0.7 toabout 1.3, and optionally from about 0.8 to about 1.1.

In certain embodiments, the functionalizing agent can be employed incombination with other coupling or terminating agents. The combinationof functionalizing agent with other terminating agent or coupling agentcan be in any molar ratio. The coupling agents that can be employed incombination with the functionalizing agent include any of those couplingagents known in the art including, but not limited to, tintetrachloride, tetraethyl ortho silicate, and tetraethoxy tin, andsilicon tetrachloride. Likewise, any terminating agent can be employedin combination with the functionalizing agent (i.e., thecyclicaminoalkoxysilane) including, but not limited to, tributyltinchloride. In certain embodiments, a proton source or quenching agent(e.g., isopropyl alcohol or water) may be added to the solution afteraddition of the functionalizing agent.

After formation of the functional polymer, a processing aid and otheroptional additives such as oil can be added to the polymer cement. Thefunctional polymer and other optional ingredients may then be isolatedfrom the solvent and optionally dried. Conventional procedures fordesolventization and drying may be employed. In one embodiment, thefunctional polymer may be isolated from the solvent by steamdesolventization or hot water coagulation of the solvent followed byfiltration. Residual solvent may be removed by using conventional dryingtechniques such as oven drying or drum drying. Alternatively, the cementmay be directly drum dried.

The functionalized polymers of this invention are particularly useful inpreparing tire components. These tire components can be prepared byusing the functionalized polymers of this invention alone or togetherwith other rubbery polymers. Other rubbery elastomers that may be usedinclude natural and synthetic elastomers. The synthetic elastomerstypically derive from the polymerization of conjugated diene monomers.These conjugated diene monomers may be copolymerized with other monomerssuch as vinyl aromatic monomers. Other rubbery elastomers may derivefrom the polymerization of ethylene together with one or more α-olefinsand optionally one or more diene monomers.

Useful rubbery elastomers include natural rubber, syntheticpolyisoprene, polybutadiene, polyisobutylene-co-isoprene, neoprene,poly(ethylene-co-propylene), poly(styrene-co-butadiene),poly(styrene-co-isoprene), and poly(styrene-co-isoprene-co-butadiene),poly(isoprene-co-butadiene), poly(ethylene-co-propylene-co-diene),polysulfide rubber, acrylic rubber, urethane rubber, silicone rubber,epichlorohydrin rubber, and mixtures thereof. These elastomers can havea myriad of macromolecular structures including linear, branched andstar shaped. Other ingredients that are typically employed in rubbercompounding may also be added.

The rubber compositions may include fillers such as inorganic andorganic fillers. The organic fillers include carbon black and starch.The inorganic fillers may include silica, aluminum hydroxide, magnesiumhydroxide, clays (hydrated aluminum silicates), and mixtures thereof.

A multitude of rubber curing agents may be employed, including sulfur orperoxide-based curing systems. Curing agents are described in 20Kirk-Othmer, Encyclopedia of Chemical Technology, 365-468, (3^(rd) Ed.1982), particularly Vulcanization Agents and Auxiliary Materials,390-402, and A.Y. Coran, Vulcanization in Encyclopedia of PolymerScience and Engineering, (2^(nd) Ed. 1989), which are incorporatedherein by reference. Vulcanizing agents may be used alone or incombination.

Other ingredients that may be employed include accelerators, oils,waxes, scorch inhibiting agents, processing aids, zinc oxide, tackifyingresins, reinforcing resins, fatty acids such as stearic acid, peptizers,and one or more additional rubbers.

These stocks are useful for forming tire components such as treads,subtreads, black sidewalls, body ply skins, bead filler, and the like.Preferably, the functional polymers are employed in tread formulations.In one or more embodiments, these tread formulations may include fromabout 10 to about 100% by weight, in other embodiments from about 35 toabout 90% by weight, and in other embodiments from about 50 to 80% byweight of the functional polymer based on the total weight of the rubberwithin the formulation. In one or more embodiments, the preparation ofvulcanizable compositions and the construction and curing of the tire isnot affected by the practice of this invention.

In one or more embodiments, the vulcanizable rubber composition may beprepared by forming an initial masterbatch that includes the rubbercomponent and filler (the rubber component optionally including thefunctionalized polymer of this invention). This initial masterbatch maybe mixed at a starting temperature of from about 25° C. to about 125° C.with a discharge temperature of about 135° C. to about 180° C. Toprevent premature vulcanization (also known as scorch), this initialmasterbatch may exclude vulcanizing agents. Once the initial masterbatchis processed, the vulcanizing agents may be introduced and blended intothe initial masterbatch at low temperatures in a final mix stage, whichpreferably does not initiate the vulcanization process. Optionally,additional mixing stages, sometimes called remills, can be employedbetween the masterbatch mix stage and the final mix stage. Variousingredients including the functionalized polymer of this invention canbe added during these remills. Rubber compounding techniques and theadditives employed therein are generally known as disclosed in Stephens,The Compounding and Vulcanization of Rubber, in Rubber Technology(2^(nd) Ed. 1973).

The mixing conditions and procedures applicable to silica-filled tireformulations are also well known as described in U.S. Pat. Nos.5,227,425, 5,719,207, 5,717,022, and European Patent No. 890,606, all ofwhich are incorporated herein by reference. In one or more embodiments,where silica is employed as a filler (alone or in combination with otherfillers), a coupling and/or shielding agent may be added to the rubberformulation during mixing. Useful coupling and shielding agents aredisclosed in U.S. Pat. Nos. 3,842,111, 3,873,489, 3,978,103, 3,997,581,4,002,594, 5,580,919, 5,583,245, 5,663,396, 5,674,932, 5,684,171,5,684,172 5,696,197, 6,608,145, 6,667,362, 6,579,949, 6,590,017,6,525,118, 6,342,552, and 6,683,135, which are incorporated herein byreference. In one embodiment, the initial masterbatch is prepared byincluding the functionalized polymer of this invention and silica in thesubstantial absence of coupling and shielding agents. It is believedthat this procedure will enhance the opportunity that the functionalizedpolymer will react or interact with silica before competing withcoupling or shielding agents, which can be added later curing remills.

Where the vulcanizable rubber compositions are employed in themanufacture of tires, these compositions can be processed into tirecomponents according to ordinary tire manufacturing techniques includingstandard rubber shaping, molding and curing techniques. Typically,vulcanization is effected by heating the vulcanizable composition in amold; e.g., it may be heated to about 140 to about 180° C. Cured orcrosslinked rubber compositions may be referred to as vulcanizates,which generally contain three-dimensional polymeric networks that arethermoset. The other ingredients, such as processing aides and fillers,may be evenly dispersed throughout the vulcanized network. Pneumatictires can be made as discussed in U.S. Pat. Nos. 5,866,171, 5,876,527,5,931,211, and 5,971,046, which are incorporated herein by reference.

In order to demonstrate the practice of the present invention, thefollowing examples have been prepared and tested. The examples shouldnot, however, be viewed as limiting the scope of the invention. Theclaims will serve to define the invention.

EXAMPLES

Experiment 1

A living polymer cement was prepared by charging a 5-gallon reactor with4.89 kg of technical hexanes, 1.20 g of a 34% solution of styrene/hexaneblend, and 7.44 kg of a 21% 1,3-butadiene/hexane blend. 2,2-bis(2′-tetrahydrofuryl)propane polar randomizer (about 0.3 equivalents perequivalent of lithium) and n-butyllithium initiator (12.05 mL of a 1.54molar solution) were subsequently charged. The reactor was heated inbatch mode to 49° C. The reaction exothermed to 65° C. within 30 minutesand batch was cooled to about 32° C. after one hour. The resultingcement was then apportioned to bottles that were dried, nitrogen purged,and ultimately capped for subsequent termination reaction. The isolatedpolymer had the following properties: Mn=100.3 kg/mol, Mw=103.7 kg/mol,and T_(g)=−31.6° C.

A first bottle of polymer cement was employed to prepare a control(Sample 1). Isopropyl alcohol was used to both terminate and coagulatethe polymer. The coagulated polymer was then drum dried.

Experiment 2

A second bottle prepared from the batch of Experiment 1 was employed toform a functionalized polymer. Specifically, 1.0 equivalent ofN-n-butyl-aza-2,2-dimethoxysilacyclopentane per equivalent of lithiumwas added to the bottle and the bottle was then agitated for 30 minutesat 50° C. The functionalized polymer was then coagulated in isopropylalcohol and drum dried. The isolated polymer had the followingproperties: M_(n)=138.9 kg/mol; M_(W)=218.6 kg/mol; and T_(g)=−31.6° C.

Experiment 3

The functionalized polymers prepared above were each employed to prepareseparate tire formulations that included either a carbon blackreinforcement or a silica and carbon black blend reinforcement (MixedSilica). The polymer portion of each sample include 100% of the samplepolymer (i.e., 100 parts by weight non-functionalized polymer wereemployed in those recipes where non-functionalized polymer was used).The recipes for the tire formulations are set forth in Table I.

TABLE I Carbon Black Mixed Silica Ingredient Formulation (phr)Formulation (phr) Polymer (functionalized 100 100 or non-functionalized)Carbon Black 55 35 Silica — 30 Antiozonant 0.95 0.95 Zinc Oxide 2.5 2.5Stearic Acid 2 1.5 Oil 10 10 Wax 1 — Coupling Agent — 4.57 Sulfur 1.31.7 Accelerators 1.9 2.25

The tire formulations were mixed using conventional mixing procedures.Namely, when preparing formulations that included carbon blackreinforcement, the ingredients (excluding the sulfur and accelerators)were initially mixed at about 133° C. at 60 r.p.m. within a Banburymixer. Sulfur and accelerators were subsequently added in a separatemixing step that was conducted at about 65° C. and 40r.p.m.

Where the formulations included both carbon black and silica, theingredients (excluding sulfur, accelerators, binder, coupling agents,and zinc oxide) were mixed at about 168° C., the coupling agent wassubsequently added and mixed at about 137° C. and 60 r.p.m., and thesulfur, accelerators, and zinc oxide were added in a subsequent mixingstep and mixed at about 95° C. and 40 r.p.m.

The formulations were then prepared into test specimens and cured withina closed cavity mold under pressure for 15 minutes at 171° C. The testspecimens were then subjected to various physical tests, and the resultsof these tests are reported in Table II. The samples designated 1A and2B included the non-functionalized polymer in the carbon blackformulation (CB) and mixed silica formulation (blend), respectively.Likewise the samples designated 2A and 2B included the functionalizedpolymer in the carbon black formulation and mixed silica formulation,respectively.

TABLE II Formulation 1A 1B 2A 2B Filler CB CB BLEND BLEND FunctionalizedPolymer No Yes No Yes ML₁₊₄ @ 130° C. 20.7 43.6 56.0 103.5 T₅ (min) 23.819.2 36.5 28.9 300% Modulus @ 23° C. 6.04 9.60 9.57 12.32 (MPa) Tensileat Break @ 8.52 11.37 14.93 18.78 23° C. (MPa) Elongation at Break @ 512356 442 428 23° C. (%) tan δ 5% @ 50° C. 0.2605 0.1570 0.2377 0.1726 ΔG′(MPa) @ 50° C. 5.120 1.204 9.593 2.729 tan δ 0.5% E, @ 0° C. 0.25320.2828 0.2264 0.3111 Shore A Peak @ 23° C. 72.4 69.9 78.6 71.9

Mooney viscosity measurement was conducted at 130° C. using a largerotor. The Mooney viscosity was recorded as the torque when the rotorhas rotated for 4 minutes. The sample is preheated at 130° C. for 1minute before the rotor starts.

The tensile mechanical properties were measured using the standardprocedure described in the ASTM-D 412 at 25° C. and 100° C. The tensiletest specimens had dumbbell shapes with a thickness of 1.9 mm. Aspecific gauge length of 25.4 mm is used for the tensile test. Heat ageddata was obtained after heating the vulcanizates for 24 hours at 100° C.

Temperature sweep experiments were conducted with a frequency of 31.4rad/sec using 0.5% strain for temperature ranging from −100° C. to −10°C., and 2% strain for the temperature ranging from −10° C. to 100° C. ΔGis the change in G′ at 0.25% from G′ at 14.00%. Payne effect (ΔG′) datawere obtained from the strain sweep experiment. A frequency of 6.28rad/sec was used for strain sweep which is conducted at 50° C. withstrain sweeping from 0.25% to 14.00%.

Various modifications and alterations that do not depart from the scopeand spirit of this invention will become apparent to those skilled inthe art. This invention is not to be duly limited to the illustrativeembodiments set forth herein.

1. A method of forming a functionalized polymer, the method comprising:reacting a living polymer with a compound defined by the formula

where R⁵ includes a monovalent organic group, R⁶ independently includesa monovalent organic group, each R⁷ independently includes hydrogen or amonovalent organic group, each R⁸ independently includes hydrogen ormonovalent organic group, R⁹ includes a hydrocarbyl group or asubstituted hydrocarbyl group, M is silicon or tin, and x includes aninteger from about 2 to about 10, where R⁵ and R⁶ may optionally eachindependently be alkoxy groups, and where R^(7,) R^(8,) and R⁹ arenon-Zerewitinoff organic groups.
 2. The method of claim 1, where theliving polymer has a glass transition temperature that is less than 0°C.
 3. The functionalized polymer of claim 2, where the living polymeris selected from the group consisting of polybutadiene, polyisoprene,poly(styrene-co-butadiene), poly(styrene-co-butadiene-co-isoprene),poly(isoprene-co-styrene), and poly(butadiene-co-isoprene).
 4. Thefunctionalized polymer of claim 2, where the living polymer has a numberaverage molecular weight of from about 5 to 1,000 kg/mol.
 5. Thefunctionalized polymer of claim 1, where the living polymer includes afunctionality or functional group at its head that reacts or interactswith rubber or rubber fillers or otherwise has a desirable impact onfilled rubber compositions or vulcanizates.
 6. The method of claim 1,where M is a silicon atom.
 7. The method of claim 1, where M is a tinatom.
 8. The method of claim 1, where R⁵ and R⁶ are each independentlyalkoxy groups.
 9. The method of claim 1, where the functionalizingcompound is selected from the group consisting ofcyclicaminodloalkoxysilanes, cyclicaminodioalkoxystannanes,cyclicaminodialkylsilanes, cyclicaminodialkylstannanes,cyclicaminoaklylalkoxysilanes, cyclicaminoalkylalkoxystannanes, andmixtures thereof.
 10. The method of claim 9, where the functionalizingcompound is selected from the group consisting ofN-methyl-aza-2,2-dimethoxysilacyclopentane,N-ethyl-aza-2,2-dimethoxysilacyclopentane,N-n-propyl-aza-2,2-dimethoxysilacyclopentane,N-n-butyl-aza-2,2-dimethoxysilacyclopentane,N-methyl-aza-2,2-diethoxysilacyclopentane,N-ethyl-aza-2,2-diethoxysilacyclopentane,N-n-propyl-aza-2,2-diethoxysilacyclopentane,N-n-butyl-aza-2,2-diethoxysilacyclopentane, N-Methyl-aza-2,2-dipropoxysilacyclopentane,N-ethyl-aza-2,2-dipropoxysilacyclopentane,N-n-propyl-aza-2,2-dipropoxysilacyclopentane,N-n-butyl-aza-2,2-dipropoxysilacyclopentane,N-rnethyl-aza-2,2-dibutoxysilacyclopentane,N-ethyl-aza-2,2-dibutoxysilacyclopentane,N-n-propyl-aza-2,2-dibutoxysilacyclopentane,N-n-butyl-aza-2,2-dibutoxysilacyclopentane,N-methyl-aza-2-ethoxy-2-methoxysilacyclopentane, N-ethyl-aza-2-butoxy-2-ethoxysilacyclopentane,N-n-propyl-aza-2-methoxy-2-propoxysilacyclopentane,N-n-butyl-aza-2-propoxy-2-ethoxysilacyclopentane, N-methylaza-2-butoxy-2-methoxysilacyclopentane,N-ethyl-aza-2-propoxy-2-ethoxysilacyclopentane,N-n-propyl-aza-2-butoxy-2-propoxysilacyclopentane, and N-n-butyl-aza-2-methoxy-2-ethoxysilacyclopentane.
 11. The method of claim 9,where the functionalizing compound is selected from the group consistingof N-methyl-aza-2,2-dimethylsilacyclopentane,N-ethyl-aza-2,2-dimethylsilacyclopentane,N-n-propyl-aza-2,2-dimethylsilacyclopentane,N-n-butyl-aza-2,2-dimethylsilacyclopentane,N-methyl-aza-2,2-diethylsilacyclopentane,N-ethyl-aza-2,2-diethylsilacyclopentane,N-n-propyl-aza-2,2-diethylsilacyclopentane,N-n-butyl-aza-2,2-diethylsilacyclopentane,N-methyl-aza-2,2-dipropylsilacyclopentane,N-ethyl-aza-2,2-dipropylsilacyclopentane,N-n-propyl-aza-2,2-dipropylsilacyclopentane,N-n-butyl-aza-2,2-dipropylsilacyclopentane,N-methyl-aza-2,2-dibutylsilacyclopentane,N-ethyl-aza-2,2-dibutylsilacyclopentane,N-n-propyl-aza-2,2-dibutylsilacyclopentane,N-n-butyl-aza-2,2-dibutylsilacyclopentane, N-methyl-aza-2-ethyl-2-methylsilacyclopentane, N-ethyl-aza-2-butyl-2-ethylsilacyclopentane,N-n-propyl-aza -2-methyl-2-propylsilacyclopentane,N-n-butyl-aza-2-propyl-2-ethylsilacyclopentane,N-methyl-aza-2-butyl-2-methylsilacyclopentane,N-ethyl-aza-2-propyl-2-ethylsilacyclopentane,N-n-propyl-aza-2-butyl-2-propylsilacyclopentane, and N-n-butyl-aza-2-methyl-2-ethylsilacyclopentane.
 12. The method of claim 9l where thefunctionalizing compound is selected from the group consisting ofN-methyl-aza-2-methoxy-2-methylsilacyclopentane,N-ethyl-aza-2-methoxy-2-methylsilacyclopentane, N-n-propylaza-2-methoxy-2-methylsilacyclopentane,N-n-butyl-aza-2-methoxy-2-methylsilacyclopentane,N-methyl-aza-2-ethoxy-2-ethylsilacyclopentane, N-ethyl-aza-2-ethoxy-2-ethylsilacyclopentane,N-n-propyl-aza-2-ethoxy-2-ethylsilacyclopentane, N-nbutyl-aza-2-ethoxy-2-ethylsilacyclopentane,N-methyl-aza-2-propoxy-2-propylsilacyclopentane,N-ethyl-aza-2-propoxy-2-propylsilacyclopentane, N-n-propylaza-2-propoxy-2-propylsilacyclopentane,N-n-butyl-aza-2-propoxy-2-propylsilacyclopentane,N-methyl-aza-2-propoxy-2-butylsilacyclopentane, N-ethyl-aza-2-propoxy-2-butylsilacyclopentane,N-n-propyl-aza-2-propoxy-2-butylsilacyclopentane, Nn-butyl-aza-2-propoxy-2-butylsilacyclopentane,N-methyl-aza-2-ethoxy-2-methylsilacyclopentane,N-ethyl-aza-2-butoxy-2-ethylsilacyclopentane, N-n-propyl-aza-2-methoxy-2-propylsilacyclopentane,N-n-butyl-aza-2-propoxy-2-ethylsilacyclopentane, Nmethyl-aza-2-butoxy-2-methylsilacyclopentane,N-ethyl-aza-2-propoxyl-2-ethylsilacyclopentane,N-n-propyl-aza-2-butoxy-2-propylsilacyclopentane, and N-n-butyl-aza-2-methoxy-2-ethylsilacyclopentane.
 13. The method of claim 9, where thefunctionalizing compound is N-methyl-aza-2,2-dimethoxysilacyclopentane.14. The method of claim 1, said step of reacting occurs within asolvent.
 15. The method of claim 1, where R⁹ is a hydrocarbyl groupselected from the group consisting of alkyl, cycloalkyl, substitutedcycloalkyl, alkenyl, cycloalkenyl, substituted cycloalkenyl, aryl,allyl, substituted aryl, aralkyl, alkaryl, and alkynyl groups.